Peroxide-glycerol explosive



Oct. 26, 1948. s, SHANLEYV ET AL 2,452,074

PEROXIDE-GLYCEROL EXPLOS IVE Filed Jan. 29, 1947 VA A AVA Y N AvA v fvvv ca 0 00/2? 1; bg VA 0 fi m VVWAAfiWM/V v A Q a W \AWX/\/\/\/\//\/\/\A/\ g;

INVENTOR. Edward 5 fian/g/ and Hans 0. Kaufman BY QM, M M v QM,

Patented Oct. 26, 1948 enomes-sweeper. EXPLOSIVE Edward S. Shanley,Grand Island, and Hans O.

Kaufimann, Eggertsville, N. I assignors to Buffalo Electro-ChemicalCompany, Inc., Tonawanda, N. Y.

Application January 29, 1947, Serial No. 725,042 2 Claims. (c1; 52 1)The present invention relates to an explosive and more particularly to acomposition containing hydrogen peroxide, water and glycerine, thecomplete composition being explodable only with a standard blasting cap,as contrasted with mechanical shock, provided the quantity of water inthe system is below a certain relatively critical figure. This is acontinuation-in-part of Serial No..643,'752, filed January 26, 1946.

Most of the liquid explosives presently in use are so sensitive to shockthat they may not be transported over the usual transportation means.Furthermore, their nature is such that complicated methods ofmanufacture practically prohibit the production of the explosive at thepoint of use. By reason of the inherent characteristics ofnitroglycerine, that material is preferred as an explosive in manytypesof operations where disruptive forces are employed as, forinstance, oil well drilling and prospecting in certain types of miningand the like, to cite but a few examples.

In all of these operations, nitroglycerine seems to be the preferredexplosive and its use has been continued even though it is wellrecognized that the use of this product is attended by an unusual hazarddue to its sensitivity to detonation by mechanical shock. Thecomplicated nature of the manufacturing process required to producenitroglycerine eliminates the possibility of manufacturing it at thepoint of use so that it must be transported by means other than theusual common carrier.

It is an object of the present invention to provide an explosivecomposition of especially high power and sensitivity which may bereadily manufactured.

It is a further object of the invention to provide an explosivecomposition which may be made at the point of use with consequentelimination of the transportation hazard.

It is a further object to provide an explosive mixture that is resistantto mechanical impact but which can be detonated only with a blastingcap.

In accordance with the present invention, hydrogen peroxide, water andglycerine may be mixed to produce a single phase liquid system in which,at room temperatures, the ingredients are relatively non-reactive. Theend product, provided the water content is maintained below about 52%and provided the amount of hydrogen peroxide is suflicient to consumethe glycerine, is a violent explosive resistant to detonation bymechanical shock but which will detonate when explosion is initiated bythe employment of a standard blasting cap.

Where the amount of water in the composition rises above about 52% byweight, the composition is not explodable with a blasting cap. Ingeneral, the explosive power of the composition is relatively moredisruptive, the less the quantity of water present. The amount ofhydrogen peroxide and glycerine employed are preferably thestoichiometric quantities necessary to provide complete combustion tocarbon dioxide and water. Explosion may, however, be obtained when theseproportions are departed from.

In order to determine the range of explosive composition, a series ofsolutions was made up from very pure hydrogen peroxide, glycerine andwater. Portions of each contained in 4 oz. glass bottles were subjectedto 22 cal. rifle fire in order to test the efiect of mechanical impact.Further portions were subjected to the action of a #6 blasting capimmersed therein. For these tests the samples were placed in test tubesconfined in heavy metal pipes. These tests are summarized in Table Ibelow.

It is to be noted that all compositions tested were immune to riflefire.

The explosive limits are shown in the attached triangular plot; Fig. 1.

All detonable compositions fall Within a roughly triangular area whosecorners have the following coordinates:

Corner A Corner B Corner 0 Per cent Per cent H101. 85+ 33 35 Per centHzO 10- 52 0 Per cent GlyeeroL 5 15 No compositions containing more thanabout 52% water can be detonated. Compositions containing somewhat lessthan 52% water can be detonated provided the glycerol and hydrogenperoxide are present in correct proportions for complete combustion ofthe glycerol to CO2 and H20. Compositions containing much less water aredetonable over a wide range of hydrogen peroxide-glycerol ratios.

Further to show the stability of glycerol-hydrogen peroxide explosive, amixture containing 5.2 ml. of 90% hydrogen-peroxide and 2:0lml. of C. P.glycerol was stored at 50 C. for 8 hours. There was no detectable lossin active oxygen content as determined by iodimetric analysis.

A similar mixture was stored for.3 days at room temperature(approximately 25? C.) Iodiometric analysis showed that 95% of theoriginalavailable oxygen was still present after thistime.

A mixture of 18 ml. glycerol and 27 "ml. of 90% hydrogen peroxide washeated in. a glass beaker over an open flame. After a time, aspluttering noise was heard and the liquid had the appearance ofboiling. Later, a jet of flame appeared above the liquid. Vigorousburning followed until the liquid was completely consumed. There was nodetonation.

Thermal calculations indicate that the peroxide explosives hereindescribed fall in the energy range of the high explosives. In general,at the optimum concentration ratio, about 1500 cal. is released per gramof mixture consumed. This figure is to be compared with 800 cal./g. forTNT and 1500 cal./g. for nitroglycerine. The performance of anexplosiveis, of course, afiected by other factors such as rate of detonation.Measurements indicate that the peroxide; mixtures actually fall in theperformance range of the high explosives.

'The action of glycerol is in contrast to the gen eral explosivecharacteristic of organic materials miscible with highly concentratedhydrogen peroxide which are explosive on mechanical shock a exemplifiedby a rifle bullet. As an example, solutions of 90% hydrogen peroxide inamounts to produce carbon dioxide and Water with the following allexploded violently on mechanical impact of a rifle bullet: methanol,ethanol, iso-' propanol, ethylene glycol, mannitol, ethyl acetate,

cane sugar, diethylene glycol, monoethyl ether,

acetone, dioxane, aniline and many others. The behavior of theglycerol-hydrogen peroxide mixture is in contrast with the generalbehavior of other organic substances.

The ready synthesis of the peroxide explosives at the point of use is ofgreat value in those cases where performance demands have heretoforecompelled the use of nitroglycerine and similar materials which must bemanufactured at a chemical plant and then transported and stored atgreat hazard.

What is claimedis:

1. An explosive, insensitive to mechanical impact but explodable with ablasting cap, which comprises glycerin, water and hydrogen peroxide,

the water constituting not more than 52% of the Glycerine 5%; hydrogenperoxide 85%; water Gly z rine 15%; hydrogen peroxide 33%; water Gl yiine 65%; hydrogen peroxide 35%; water EDWARD s. SHANLEY. HANS O.KAUFFIVIANN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number

